Hair conditioning compositions

ABSTRACT

An aqueous hair conditioner composition comprising: a) a cationic conditioning surfactant, b) discrete, dispersed droplets comprising a water-insoluble conditioning oil and c) a block copolymer with a mean molecular weight of 1000 unified atomic mass units or more, comprising polyethyleneoxide and polypropyleneoxide blocks selected from the group consisting of (i) poloxamers according to formula (I), wherein the mean value of (y) is from 18 to 60 and the mean value (x) is from 7 to 140 such that the mean value of the ratio (x/y) is from 0.4 to 3.0 and (ii) poloxamines according to formula (II), wherein the mean value of (a) is 2 or more and the mean value of (b) is 2 or more.

TECHNICAL FIELD

The invention is concerned with hair-conditioning compositions. It isparticularly concerned with hair conditioner compositions, which areapplied to the hair after washing or shampooing and subsequent rinsing.More specifically, it is concerned with improving the deposition ofconditioning oil onto the tip region of hair, from hair conditionercompositions which contain dispersed hydrophobic conditioning oildroplets.

BACKGROUND AND PRIOR ART

Hair conditioner compositions which provide conditioning to the hair arewell known in the art. Such compositions comprise one or moreconditioning agents. The purpose of the conditioning agent is to makethe hair easier to comb when wet and more manageable when dry, e.g. lessstatic and fly-away. They also make the hair feel softer. Typically,these conditioning agents are either water-insoluble oily materialswhich act by spreading on the hair in the form of a film, or cationicsurfactant materials or polymers, which adsorb onto the hair surface.

Hair conditioners can be in the form of rinse-off conditioners (usuallyapplied to the hair after shampooing as a liquid or mousse) or leave-onproducts such as hair oils or serums, mousses and styling products.

Typically, water-insoluble oily conditioning materials are dispersed inaqueous products in the form of small droplets or particles in order tofacilitate the stability of the dispersion to phase separation and toenhance the deposition of the oily material onto the hair.

A preferred water-insoluble oily conditioning material is based onsilicone polymers, preferably polydimethylsiloxanes, with or withoutvarious functionalising groups. Non-silicone conditioning oils includehydrocarbon oils and triglycerides.

Although these cationic surfactants, cationic polymers andwater-insoluble oily conditioning materials provide conditioning effectsto the hair, it is desirable to improve the conditioning effectsobtainable from them.

Natural oils secreted by the sebaceous gland at the base of the hairlead to hair being more hydrophobic near the root rather than near thetip. This means that droplets of hydrophobic conditioning oil depositedonto hair are more likely to spread and form films on the hair at thebase of the hair rather than near the tip of the hair, and this is foundin practice.

Certain consumers find the effects arising from this effect to beundesirable in that it may lead to the hair feeling greasy at the rootsor heavy and dull.

In attempts to overcome the problems in the prior art, it has beenconsidered desirable to target the deposition of the conditioning oildroplets onto the tip regions of the hair in preference to the basalregions, and much research has been carried out in this field of work.Although it would be desirable to make the surface of the oil dropletsmore hydrophilic, it had always been considered that the high levels ofcationic surfactant in rinse-off hair conditioner compositions woulddominate the surface chemistry and hydrophilicity of the oil droplets.Thus the conventional view is that irrespective of any additives addedto the conditioning oil droplets, the conditioning surfactant wouldcontrol the droplet hydrophilicity and deposition.

It has now surprisingly been found, that by blending certain types ofsurface active block copolymers of a high molecular weight withconditioning oil emulsion droplets, enhanced deposition of the dropletsonto the tip regions of hairs can be achieved. Although not wishing tobe bound by the scientific reasoning underlying this phenomenon, itseems that surface active polymer remains at the droplet surface, evenin the presence of other surfactant molecules from the conditioner,making the droplets more hydrophilic than the droplets in conventionaloil droplet-containing hair conditioner compositions. This leads toimproved deposition of the droplets towards the more hydrophilic tipregion of the hair.

The present invention concerns the use of Poloxamers (CTFA designation)to enhance the deposition of hydrophobic conditioning oil onto the hairtip region from hair conditioner compositions, particularly fromrinse-off conditioner compositions.

U.S. Pat. No. 3,753,916 discloses the use of cationic polymers asdeposition aids for conditioning oils. Poloxamers are mentioned underthe trade name Pluronic as optional ingredients.

WO 92/14440 discloses Pluronics (Poloxamers) in anti-dandruff shampoosas one of a class of ‘synergisers’ that unexpectedly enhanceanti-dandruff efficacy.

WO 96/17590 discloses personal washing compositions containing lipids asthe conditioning phase. The lipids are emulsified with a nonionicemulsifier. Poloxamers are listed as one of the possible polyalkoxynonionic emulsifiers with HLB (hydrophile lipophile balance) in therange 1 to 15.

U.S. Pat. No. 5,100,657 lists Pluronics (Poloxamers) as optionalingredients in hair conditioner compositions.

SUMMARY OF THE INVENTION

In a first aspect, the invention provides an aqueous hair conditionercomposition comprising:

-   -   a) a cationic conditioning surfactant,    -   b) discrete, dispersed droplets comprising a water insoluble        conditioning oil and    -   c) a block copolymer with a mean molecular weight of 1000        unified atomic mass units or more, comprising polyethyleneoxide        and polypropyleneoxide blocks selected from the group consisting        of (i) poloxamers according to formula I:        wherein the mean value of y is from 18 to 60 and the mean value        x is from 7 to 140 such that the mean value of the ratio x/y is        from 0.4 to 3.0. and (ii) poloxamines according to formula II:        wherein the mean value of a is 2 or more and the mean value of b        is 2 or more.

DETAILED DESCRIPTION

Compositions in accordance with the invention are formulated ascompositions for applying to the hair and subsequent rinsing such ashair conditioner or conditioner mousse or gel.

By tip region of the hair is meant the distal half of each individualhair.

Surface Active Polymer

An essential component of compositions according to the invention is asurface active block copolymer. This is a block copolymer based onpolyethyleneoxide (EO) and polypropyleneoxide (PO) blocks. Suitably, themean molecular weight of the block copolymer is 1000 unified atomic massunits or more, preferably 2000 or more, more preferably 4000 or more,most preferably 8000 or more.

The mean molecular weight is suitably measured by determining thehydroxyl number for the polymer then transforming this into molecularweight. This corresponds to a number based mean molecular weight.

Suitable EO/PO block copolymers according to formula I have the CTFAdesignation Poloxamer.

These are commercially available under the trade name “Pluronic” fromBASF. Suitably, the mean value of y is from 18 to 60, preferably from 30to 60. The mean value x is from 7 to 140 such that the ratio x/y is from0.4 to 3.0, preferably from 1.0 to 2.7.

In formula I, the degree of polymerisation, x, is indicated as the samefor each polyethyleneoxide block. For the sake of clarity, it should beexplained that these degrees of polymerisation are mean values and areapproximately the same rather than identical for any particular formula.

This is a result of the polymerisation methods used for production ofthe compounds.

Another suitable block copolymer is according to formula II and has theCTFA designation “Poloxamine”.

Poloxamines are commercially available from BASF under the trade name“Tetronic”. Suitably the mean value of a is 2 or more and the mean valueof b is 2 or more.

Preferably, the mean value of a is 3 or more and the mean value of b is3 or more. It is also preferred if the ratio a/b is from 0.1 to 15, morepreferably from 0.5 to 6.

In formula II, the degrees of polymerisation, a and b are indicated asthe same for each polyethyleneoxide and polypropylene blockrespectively. For the sake of clarity, it should be explained that thesedegrees of polymerisation are mean values and are approximately the samerather than identical for any particular formula. This is a result ofthe polymerisation methods used for production of the compounds.Suitably, the level of surface active block copolymer is from 0.005% to5% by weight of the composition, preferably from 0.01% to 2%, morepreferably from 0.01% to 0.7%, even more preferably from 0.01% to 0.4%.

Conditioning Oil

An essential component of compositions according to the invention is ahydrophobic conditioning oil. In order for such an oil to exist indiscrete droplets in the compositions according to the invention, itmust be water-insoluble. By water-insoluble is meant that the solubilityin water at 25° C. is 0.01% by weight or less.

It is preferred if the conditioning oil is non-volatile, by which it ismeant that the vapour pressure of the oil at 25° C. is less than 10 Pa.

As used herein, the term “conditioning oil” includes any material, whichis used to give a particular conditioning benefit to hair. For example,suitable materials are those which deliver one or more benefits relatingto shine, softness, combability, wet-handling, anti-static properties,protection against damage, body, volume, stylability and manageability.

Preferred conditioning oils will have a viscosity of less than 5 Pa.s,more preferably less than 1 Pa.s, and most preferably less than 0.5Pa.s, e.g. 0.1 Pa.s and under as measured at 25° C. at a shear rate of 1sec⁻¹. Oily and fatty materials with higher viscosities may be used. Forexample, materials with viscosities as high as 65 Pa.s may be used.

Suitable hydrophobic conditioning oils are selected from hydrocarbonoils, fatty esters, silicone oils and mixtures thereof.

Hydrocarbon oils include cyclic hydrocarbons, straight chain aliphatichydrocarbons (saturated or unsaturated), and branched chain aliphatichydrocarbons (saturated or unsaturated). Straight chain hydrocarbon oilswill preferably contain from about 12 to about 30 carbon atoms. Branchedchain hydrocarbon oils can and typically may contain higher numbers ofcarbon atoms. Also suitable are polymeric hydrocarbons of alkenylmonomers, such as C₂-C₆ alkenyl monomers. These polymers can be straightor branched chain polymers. The straight chain polymers will typicallybe relatively short in length, having a total number of carbon atoms asdescribed above for straight chain hydrocarbons in general. The branchedchain polymers can have substantially higher chain length. The numberaverage molecular weight of such materials can vary widely, but willtypically be up to about 2000, preferably from about 200 to about 1000,more preferably from about 300 to about 600.

Specific examples of suitable hydrocarbon oils include paraffin oil,mineral oil, saturated and unsaturated dodecane, saturated andunsaturated tridecane, saturated and unsaturated tetradecane, saturatedand unsaturated pentadecane, saturated and unsaturated hexadecane, andmixtures thereof. Branched-chain isomers of these compounds, as well asof higher chain length hydrocarbons, can also be used. Exemplarybranched-chain isomers are highly branched saturated or unsaturatedalkanes, such as the permethyl-substituted isomers, e.g., thepermethyl-substituted isomers of hexadecane and eicosane, such as2,2,4,4,6,6,8,8-dimethyl-10-methylundecane and2,2,4,4,6,6-dimethyl-8-methylnonane, sold by Permethyl Corporation. Afurther example of a hydrocarbon polymer is polybutene, such as thecopolymer of isobutylene and butene. A commercially available materialof this type is L-14 polybutene from Amoco Chemical Co. (Chicago, Ill.,U.S.A.).

Particularly preferred hydrocarbon oils are the various grades ofmineral oils. Mineral oils are clear oily liquids obtained frompetroleum oil, from which waxes have been removed, and the more volatilefractions removed by distillation. The fraction distilling between 250°C. to 300° C. is termed mineral oil, and it consists of a mixture ofhydrocarbons ranging from C₁₆H₃₄ to C₂₁H₄₄. Suitable commerciallyavailable materials of this type include Sirius M85 and Sirius M125, allavailable from Silkolene.

Suitable fatty esters are characterised by having at least 10 carbonatoms, and include esters with hydrocarbyl chains derived from fattyacids or alcohols, e.g., monocarboxylic acid esters, polyhydric alcoholesters, and di- and tricarboxylic acid esters. The hydrocarbyl radicalsof the fatty esters hereof can also include or have covalently bondedthereto other compatible functionalities, such as amides and alkoxymoieties, such as ethoxy or ether linkages. Monocarboxylic acid estersinclude esters of alcohols and/or acids of the formula R′COOR in whichR′ and R independently denote alkyl or alkenyl radicals and the sum ofcarbon atoms in R′ and R is at least 10, preferably at least 20.

Specific examples include, for example, alkyl and alkenyl esters offatty acids having aliphatic chains with from about 10 to about 22carbon atoms, and alkyl and/or alkenyl fatty alcohol carboxylic acidesters having an alkyl and/or alkenyl alcohol-derived aliphatic chainwith about 10 to about 22 carbon atoms, benzoate esters of fattyalcohols having from about 12 to 20 carbon atoms.

The monocarboxylic acid ester need not necessarily contain at least onechain with at least 10 carbon atoms, so long as the total number ofaliphatic chain carbon atoms is at least 10. Examples include isopropylisostearate, hexyl laurate, isohexyl laurate, isohexyl palmitate,isopropyl palmitate, decyl oleate, isodecyl oleate, hexadecyl stearate,decyl stearate, isopropyl isostearate, dihexyldecyl adipate, lauryllactate, myristyl lactate, cetyl lactate, oleyl stearate, oleyl oleate,oleyl myristate, lauryl acetate, cetyl propionate, and oleyl adipate.

Di- and trialkyl and alkenyl esters of carboxylic acids can also beused. These include, for example, esters of C₄-C₈ dicarboxylic acidssuch as C₁-C₂₂ esters (preferably C₁-C₆) of succinic acid, glutaricacid, adipic acid, hexanoic acid, heptanoic acid, and octanoic acid.Examples include diisopropyl adipate, diisohexyl adipate, anddiisopropyl sebacate. Other specific examples include isocetyl stearoylstearate, and tristearyl citrate.

Polyhydric alcohol esters include alkylene glycol esters, for exampleethylene glycol mono and di-fatty acid esters, diethylene glycol mono-and di-fatty acid esters, polyethylene glycol mono- and di-fatty acidesters, propylene glycol mono- and di-fatty acid esters, polypropyleneglycol monooleate, polypropylene glycol monostearate, ethoxylatedpropylene glycol monostearate, polyglycerol poly-fatty acid esters,ethoxylated glyceryl monostearate, 1,3-butylene glycol monostearate,1,3-butylene glycol distearate, polyoxyethylene polyol fatty acid ester,sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid estersand mono-, di-and triglycerides.

Particularly preferred fatty esters are mono-, di- and triglycerides,more specifically the mono-, di-, and tri-esters of glycerol and longchain carboxylic acids such as C₁-C₂₂ carboxylic acids. A variety ofthese types of materials can be obtained from vegetable and animal fatsand oils, such as coconut oil, castor oil, safflower oil, sunflower oil,cottonseed oil, corn oil, olive oil, cod liver oil, almond oil, avocadooil, palm oil, sesame oil, peanut oil, lanolin and soybean oil.Synthetic oils include triolein and tristearin glyceryl dilaurate.

Specific examples of preferred materials include cocoa butter, palmstearin, sunflower oil, soyabean oil and coconut oil.

The oil may be blended with other materials in the discrete dropletspresent in compositions according to the invention.

It is preferred that the d(0.5) volume-based median particle diameter ofthe hydrophobic conditioning oil droplets in the composition is lessthan 100 micrometres, more preferably less than 40 micrometres, evenmore preferably less than 10 micrometres and most preferably less than 6micrometres. Larger particle diameters lead to problems in stabilisingthe composition from separation of components. Practical difficulties inmaking emulsion droplets with a median diameter of 0.02 micrometres orless are known to those skilled in the art. Thus it is preferred if thevolume-based median diameter d(0.5) is greater than 0.02 micrometres,more preferably greater than 0.03 micrometres, even more preferablygreater than 0.1 micrometres. Preferred ranges of median diameter can beformed by combining any of the preferred minimum diameters with any ofthe preferred maximum diameters. Volume-based median droplet diameterd(0.5) may be measured by means of a laser light scattering technique,for example using a 2600D Particle Sizer from Malvern Instruments.

The total amount of hydrophobic conditioning oil present in thecomposition is preferably from 0.1% to 10% by weight of the totalcomposition more preferably from 0.2% to 6%, most preferably 0.5% to 4%.

Silicone Conditioning Oils

Preferred hydrophobic conditioning oils for use in compositionsaccording to the invention are silicones.

Suitable silicones for use as conditioning oils includepolydiorganosiloxanes, in particular polydimethylsiloxanes which havethe CTFA designation dimethicone. Also suitable for use in compositionsof the invention are polydimethyl siloxanes having hydroxyl end groups,which have the CTFA designation dimethiconol.

It is preferred if the silicone oil also comprises a functionalisedsilicone. Suitable functionalised silicones include, for example,amino-, carboxy-, betaine-, quaternary ammonium-, carbohydrate-,hydroxy- and alkoxy-substituted silicones. Preferably, thefunctionalised silicone contains multiple substitutions.

For the avoidance of doubt, as regards hydroxyl-substituted silicones, apolydimethylsiloxane merely having hydroxyl end groups (which have theCTFA designation dimethiconol) is not considered a functionalisedsilicone within the present invention. However, a polydimethylsiloxanehaving hydroxyl substitutions along the polymer chain is considered afunctionalised silicone.

Preferred functionalised silicones are amino-functionalised silicones.Suitable amino functionalised silicones are described in EP 455,185(Helene Curtis) and include trimethylsilylamodimethicone as depictedbelow, and are sufficiently water insoluble so as to be useful incompositions of the invention:Si(CH₃)₃—O—[Si(CH₃)₂—O—]_(x)—[Si(CH₃)(R—NH—CH₂CH₂NH₂)—O—]_(y)—Si(CH₃)₃wherein x 30 y is a number from about 50 to about 500, and the weightpercent amine functionality is in the range of from about 0.03% to about8% by weight of the molecule, and wherein R is an alkylene group havingfrom 2 to 5 carbon atoms. Preferably, the number x+y is in the range offrom about 100 to about 300, and the weight percent amine functionalityis in the range of from about 0.03% to 8% by weight of the molecule.

As expressed here, the weight percent amine functionality is measured bytitrating a sample of the amino-functionalised silicone againstalcoholic hydrochloric acid to the bromocresol green end point. Theweight percent amine is calculated using a molecular weight of 45(corresponding to CH₃—CH₂—NH₂).

Suitably, the weight percent amine functionality measured and calculatedin this way is in the range from 0.03% to 8%, preferably from 0.5% to4%.

An example of a commercially available amino-functionalised siliconeuseful in the silicone component of the composition of the invention isDC-8566 available from Dow Corning (INCI name: dimethyl,methyl(aminoethylaminoisobutyl) siloxane). This has a weight percent aminefunctionality of about 1.4%.

By “amino functional silicone” is meant a silicone containing at leastone primary, secondary or tertiary amine group, or a quaternary ammoniumgroup. Examples of suitable amino functional silicones include:polysiloxanes having the CTFA designation “amodimethicone”. Specificexamples of amino functional silicones suitable for use in the inventionare the aminosilicone oils DC-8220, DC-8166, DC-8466, and DC-8950-114(all ex Dow Corning), and GE 1149-75, (ex General Electric Silicones).Suitable quaternary silicone polymers are described in EP-A-0 530 974. Apreferred quaternary silicone polymer is K3474, ex Goldschmidt.

Another preferred functional silicone for use as a component in thehydrophobic conditioning oil is an alkoxy-substituted silicone. Suchmolecules are known as silicone copolyols and have one or morepolyethyleneoxide or polypropyleneoxide groups bonded to the siliconepolymer backbone, optionally through an alkyl linking group.

A non-limiting example of a type of silicone copolyol useful incompositions of the invention has a molecular structure according to theformula depicted below:Si(CH₃)₃[O—Si(CH₃)(A)]_(p)—[O—Si(CH₃)(B)]_(q)—O—Si(CH₃)_(3.)

In this formula, A is an alkylene chain with from 1 to 22 carbon atoms,preferably 4 to 18, more preferably 10 to 16. B is a group with thestructure: —(R)-(EO)_(r)(PO)_(s)—OH wherein R is a linking group,preferably an alkylene group with 1 to 3 carbon atoms. Preferably R is—(CH₂)₂—. The mean values of r and s are 5 or more, preferably 10 ormore, more preferably 15 or more. It is preferred if the mean values ofr and s are 100 or less. In the formula, the value of p is suitably 10or more, preferably 20 or more, more preferably 50 or more and mostpreferably 100 or more. The value of q is suitably from 1 to 20 whereinthe ratio p/q is preferably 10 or more, more preferably 20 or more. Thevalue of p +q is a number from 11 to 500, preferably from 50 to 300.

Suitable silicone copolyols have an HLB of 10 or less, preferably 7 orless, more preferably 4 or less. A suitable silicone copolyol materialis DC5200, known as Lauryl PEG/PPG-18/18 methicone (INCI name),available from Dow Corning.

It is preferred to use a combination of functional and non-functionalsilicones as the hydrophobic silicone conditioning oil. Preferably thesilicones are blended into common droplets prior to incorporation intocompositions according to the invention.

The viscosity of the droplets hydrophobic silicone conditioning oil,measured in isolation from the rest of the composition (i.e. not theviscosity of any pre-formed emulsion, but of the hydrophobicconditioning oil itself) is typically from 350 to 200,000,000 mm²sec⁻¹at 25° C. Preferably the viscosity is at least 5,000 mm²sec⁻¹ at 25° C.,more preferably at least 10,000 mm²sec⁻¹. Preferably the viscosity doesnot exceed 20,000,000 mm²sec⁻¹, more preferably 10,000,000 mm²sec⁻¹,most preferably 5,000,000 mm²sec⁻¹.

Suitable methods for measuring the kinematic viscosity of silicone oilsare known to those skilled in the art, e.g. capillary viscometers. Forhigh viscosity silicones, a constant stress rheometer can also be usedto measure dynamic viscosity which is related to kinematic viscosity bythe density of the silicone. The viscosity should be measured at lowshear rates, typically less than 10 s⁻¹, such that the silicone exhibitsNewtonian behaviour (i.e. viscosity independent of shear rate).

Conditioning Surfactant

Hair conditioner compositions according to the invention comprise one ormore conditioning surfactants which are cosmetically acceptable andsuitable for topical application to the hair.

Suitable conditioning surfactants are selected from cationicsurfactants, used singly or in admixture. Cationic surfactants useful incompositions of the invention contain amino or quaternary ammoniumhydrophilic moieties which are positively charged when dissolved in theaqueous composition of the present invention.

Examples of suitable cationic surfactants are those corresponding to thegeneral formula:[N(R₁)(R₂)(R₃)(R₄)]⁺(X)⁻in which R₁, R₂, R₃, and R₄ are independently selected from (a) analiphatic group of from 1 to 22 carbon atoms, or (b) an aromatic,alkoxy, polyoxyalkylene, alkylamido, hydroxyalkyl, alkoylalkyl, aryl oralkylaryl group having up to 22 carbon atoms; and X is a salt-forminganion such as those selected from halogen, (e.g. chloride, bromide),acetate, citrate, lactate, glycolate, phosphate nitrate, sulphate, andalkylsulphate radicals.

The aliphatic groups can contain, in addition to carbon and hydrogenatoms, ether linkages, and other groups such as amino groups. The longerchain aliphatic groups, e.g., those of about 12 carbons, or higher, canbe saturated or unsaturated.

Preferred cationic surfactants for conditioner compositions of thepresent invention are so-called monoalkyl quaternary ammonium compoundsin which R₁ has an alkyl chain length from C16 to C22 and R₂, R₃ and R₄have 2 or less carbon atoms.

Other preferred cationic surfactants are so-called dialkyl quaternaryammonium compounds in which R₁ and R₂ independently have an alkyl chainlengths from C16 to C22 and R₃ and R₄ have 2 or less carbon atoms.

Examples of suitable cationic surfactants include quaternary ammoniumcompounds, particularly trimethyl quaternary compounds.

Preferred quaternary ammonium compounds include cetyltrimethylammoniumchloride, behenyltrimethylammonium chloride (BTAC), cetylpyridiniumchloride, tetramethylammonium chloride, tetraethylammonium chloride,octyltrimethylammonium chloride, dodecyltrimethylammonium chloride,hexadecyltrimethylammonium chloride, octyldimethylbenzylammoniumchloride, decyldimethylbenzylammonium chloride,stearyldimethylbenzylammonium chloride, didodecyldimethylammoniumchloride, dioctadecyldimethylammonium chloride, tallowtrimethylammoniumchloride, cocotrimethylammonium chloride, PEG-2 oleylammonium chlorideand salts of these, where the chloride is replaced by halogen, (e.g.,bromide), acetate, citrate, lactate, glycolate, phosphate nitrate,sulphate, or alkylsulphate. Further suitable cationic surfactantsinclude those materials having the CTFA designations Quaternium-5,Quaternium-31 and Quaternium-18. Mixtures of any of the foregoingmaterials may also be suitable. Particularly useful quaternary ammoniumcationic surfactants for use in hair conditioners of the invention arecetyltrimethylammonium chloride, available commercially, for example asGENAMIN CTAC, ex Hoechst Celanese and Arquad 16/29 supplied by AkzoNobel, and behenyltrimethylammonium chloride (BTAC) such as GenaminKDM-P supplied by Clariant.

Another suitable cationic conditioning surfactant is a dialkoylalkyldimethylammonium halide. An example of such a compound has the CTFAdesignation dipalmitoyethyldimethylammonium chloride.

Further suitable cationic systems are primary, secondary, and tertiaryfatty amines used in combination with an acid to provide the cationicspecies. The alkyl groups of such amines preferably have from 12 to 22carbon atoms, and can be substituted or unsubstituted.

Particularly useful are amido substituted tertiary fatty amines, inparticular tertiary amines having one C₁₂ to C₂₂ alkyl or alkenyl chain.Such amines, useful herein, include stearamidopropyidimethylamine,stearamidopropyidiethylamine, stearamidoethyldiethylamine,stearamidoethyldimethylamine, palmitamidopropyldimethylamine,palmitamidopropyldiethylamine, palmitamidoethyldiethylamine,palmitamidoethyldimethylamine, behenamidopropyldimethylamine,behenamidopropyldiethylamine, behenamidoethyldiethylamine,behenamidoethyldimethylamine, arachidamidopropyldimethylamine,arachidamidopropyldiethylamine, arachidamidoethyldiethylamine,arachidamidoethyldimethylamine, diethylaminoethylstearamide.

Also useful are dimethylstearamine, dimethylsoyamine, soyamine,myristylamine, tridecylamine, ethylstearylamine, N-tallowpropanediamine, ethoxylated (with 5 moles of ethylene oxide) stearylamine,dihydroxyethylstearylamine, and arachidyl behenylamine.

As stated previously, these amines are typically used in combinationwith an acid to provide the cationic species. The preferred acid usefulherein includes L-glutamic acid, lactic acid, hydrochloric acid, malicacid, succinic acid, acetic acid, fumaric acid, tartaric acid, citricacid, L-glutamic hydrochloride, and mixtures thereof; more preferablyL-glutamic acid, lactic acid, citric acid. Cationic amine surfactantsincluded among those useful in the present invention are disclosed inU.S. Pat. No. 4,275,055 to Nachtigal, et al., issued Jun. 23, 1981.

The molar ratio of protonatable amines to H⁺ from the acid is preferablyfrom about 1:0.3 to 1:1.2, and more preferably from about 1:0.5 to about1:1.1.

In the conditioners of the invention, the level of cationic surfactantis preferably from 0.01 to 10, more preferably 0.05 to 5, mostpreferably 0.1 to 4 percent by weight of the total composition.

Fatty Materials

Conditioner compositions of the invention preferably additionallycomprise fatty materials. The combined use of fatty materials andcationic surfactants in conditioning compositions is believed to beespecially advantageous, because this leads to the formation of astructured lamellar or liquid crystal phase, in which the cationicsurfactant is dispersed.

By “fatty material” is meant a fatty alcohol, an alkoxylated fattyalcohol, a fatty acid or a mixture thereof. Preferably, the alkyl chainof the fatty material is fully saturated.

Representative fatty materials comprise from 8 to 22 carbon atoms, morepreferably 16 to 22. Examples of suitable fatty alcohols include cetylalcohol, stearyl alcohol and mixtures thereof. The use of thesematerials is also advantageous in that they contribute to the overallconditioning properties of compositions of the invention.

Alkoxylated, (e.g. ethoxylated or propoxylated) fatty alcohols havingfrom about 12 to about 18 carbon atoms in the alkyl chain can be used inplace of, or in addition to, the fatty alcohols themselves. Suitableexamples include ethylene glycol cetyl ether, polyoxyethylene (2)stearyl ether, polyoxyethylene (4) cetyl ether, and mixtures thereof.

The level of fatty material in conditioners of the invention is suitablyfrom 0.01 to 15, preferably from 0.1 to 10, and more preferably from 0.5to 4 percent by weight of the total composition. The weight ratio ofcationic surfactant to fatty alcohol is suitably from 10:1 to 1:10,preferably from 4:1 to 1:8, optimally from 1:1 to 1:7, for example 1:3.

Adjuvants

The compositions of the present invention may also contain adjuvantssuitable for hair care. Generally such ingredients are includedindividually at a level of up to 2%, preferably up to 1% by weight ofthe total composition.

Among suitable hair care adjuvants, are natural hair root nutrients,such as amino acids and sugars. Examples of suitable amino acids includearginine, cysteine, glutamine, glutamic acid, isoleucine, leucine,methionine, serine and valine, and/or precursors and derivativesthereof. The amino acids may be added singly, in mixtures, or in theform of peptides, e.g. di- and tripeptides. The amino acids may also beadded in the form of a protein hydrolysate, such as a keratin orcollagen hydrolysate. Suitable sugars are glucose, dextrose andfructose. These may be added singly or in the form of, e.g. fruitextracts. A particularly preferred combination of natural hair rootnutrients for inclusion in compositions of the invention is isoleucineand glucose. A particularly preferred amino acid nutrient is arginine.Another suitable adjuvant is glycolic acid.

Optional Ingredients

Compositions of this invention may contain any other ingredient normallyused in hair treatment formulations. These other ingredients may includeviscosity modifiers, preservatives, colouring agents, polyols such asglycerine and polypropylene glycol, chelating agents such as EDTA,antioxidants, fragrances, antimicrobials and sunscreens. Each of theseingredients will be present in an amount effective to accomplish itspurpose. Generally these optional ingredients are included individuallyat a level of up to 5% by weight of the total composition.

Preparation of Compositions

One method for preparing compositions according to the invention is toadd hydrophobic conditioning oil to the other components comprising thehair conditioner composition, followed by suitable mixing of thecomposition in order to ensure that the blend is dispersed as dropletsof a suitable size.

However it is preferred if the hydrophobic conditioning oil is firstformed into an aqueous emulsion prior to incorporation into the hairconditioner composition. Thus another aspect of the invention is amethod for preparing an aqueous hair conditioner composition comprisingthe steps of:

-   -   i) preparing a solution comprising water and the surface active        block copolymer,.    -   ii) adding a water-insoluble conditioning oil to the solution,    -   iii) forming the solution and the conditioning oil into an        oil-in-water emulsion by high-shear mixing,    -   iv) dispersing the oil-in-water emulsion comprising the block        copolymer into a hair conditioner composition.

Another preferred method for preparing a hair conditioning compositionaccording to the invention comprises the steps of:

-   -   i) preparing an oil-in-water emulsion of a water-insoluble        conditioning oil,    -   ii) dispersing the surface active block copolymer into the        emulsion,    -   iii) dispersing said oil-in-water emulsion comprising the block        copolymer into a hair conditioner composition.

Suitable emulsifiers for use in the preparation of the aqueous emulsionare well known in the art and include anionic, cationic, zwitterionic,amphoteric and nonionic surfactants, and mixtures thereof. Examples ofanionic surfactants used as emulsifiers for the conditioning oilparticles are alkylarylsulphonates, e.g., sodium dodecylbenzenesulphonate, alkyl sulphates e.g., sodium lauryl sulphate, alkyl ethersulphates, e.g., sodium lauryl ether sulphate nEO, where n is from 1 to20, alkylphenol ether sulphates, e.g., octylphenol ether sulphate nEOwhere n is from 1 to 20, and sulphosuccinates, e.g., sodiumdioctylsulphosuccinate.

Examples of nonionic surfactants suitable for use as emulsifiers for theconditioning oil droplets are alkylphenol ethoxylates, e.g., nonylphenolethoxylate nEO, where n is from 1 to 50 and alcohol ethoxylates, e.g.,lauryl alcohol nEO, where n is from 1 to 50, ester ethoxylates, e.g.,polyoxyethylene monostearate where the number of oxyethylene units isfrom 1 to 30.

A preferred process for preparing oil-in-water emulsions of the dropletscomprising the hydrophobic conditioning oil, which can then beincorporated in the hair treatment compositions, involves use of amixer. Depending upon the viscosity of the conditioning oil, a suitablemixer should be chosen so as to provide sufficient shear to give therequired final particle size of the emulsion. Examples of suitablebenchtop mixers spanning the range of necessary shear are HeidolphRZR2100, Silverson L4R, Rannie mini-lab high pressure homogeniser andYstral X10/20-750. Other mixers of similar specification are well knownto those skilled in the art and can also be used in this application.Equally it is possible to manufacture oil-in-water emulsions of thisdescription on larger scale mixers which offer similar shear regimes tothose described above.

It is also possible to produce suitable emulsions, for use incompositions according to the invention, by means of emulsionpolymerisation of the silicone rather than by mechanical emulsification.In this case a preferred process is to add the block copolymer to theemulsion after emulsion polymerisation before combining the blend ofemulsion and block copolymer with the rest of the composition.Preferably, the mixer is also capable of controlling the temperature ofthe components during mixing, e.g. it comprises a jacket through which aheat transfer fluid can be circulated.

It is preferred if the aqueous phase of the emulsion contains apolymeric thickening agent to prevent phase separation of the emulsionafter preparation. Preferred thickening agents are cross-linkedpolyacrylates, cellulosic polymers or derivatives of cellulosicpolymers.

Mousses

Hair conditioner compositions in accordance with the invention may alsotake the form of aerosol foams (mousses) in which case a propellant maybe included in the composition. This agent is responsible for expellingthe other materials from the container and forming the hair moussecharacter.

The propellant gas can be any liquefiable gas conventionally used foraerosol containers. Examples of suitable propellants include dimethylether, propane, n-butane and isobutane, used singly or in admixture.

The amount of the propellant gases is governed by normal factors wellknown in the aerosol art. For hair mousses, the level of propellant isgenerally from 3 to 30, preferably from 5 to 15% by weight of the totalcomposition.

Alternatively, the mousse may be generated mechanically without the needfor a propellant by use of a suitable foam-generating container.

Mode of Use

The compositions of the invention are primarily intended for topicalapplication to the hair and/or scalp and or skin of a human subject asrinse-off treatments to improve hair fibre surface properties such assmoothness, softness, manageability, cuticle integrity, and shine. Inparticular, compositions according to the invention are used forimproving the deposition of conditioning oil onto the tip region ofhair.

Thus another aspect of the invention is a method for enhancingdeposition of water-insoluble conditioning oil from a hair-conditionercomposition onto the hair tip region by applying to the hair acomposition according to the invention followed by rinsing with water.

A further aspect of the invention is the use of a composition accordingto the invention for enhancing deposition of water-insolubleconditioning oil onto the tip region of hair.

The invention is further demonstrated with reference to the following,non-limiting examples:

EXAMPLES

Various hair conditioner compositions were prepared using as a basis theformulation in table 1. TABLE 1 Weight % (as 100% Chemical NameTradename active) Behenyl Genamin KDMP 2.0 trimethylammonium (85%active) chloride Cetearyl Alcohol Laurex 4.0 Preservative Nipagen M 0.2Silicone DC1785 3.0 Polaxamer Pluronic (see table 2) 0.09 Water — to 100

Examples 1 to 9 and B, C and D were made up using the relevant Polaxameras detailed in table 2. Example A was made up without Polaxamer present.

Examples A to D are comparative examples outside the scope of theinvention whereas examples 1 to 9 are according to the invention.

Test Method

0.25g/5 cm switches of tip hair which had been cleaned with a solutionof 14% SLES 2EO and 2% cocoamidopropyl betaine in water followed byextensive rinsing, were used for this experiment. The test hairconditioner composition was diluted to 1 in 5 by weight with distilledwater and stirred throughout with a magnetic stirrer. 5 switches wereplaced in one half of a petri dish. 1.5 mls of diluted hair conditionerwas placed along the length of the switches which were then agitated inthe dish for 30 seconds, followed by a rinse for 30 seconds under tapwater (12° French hard) at 40° C., with a flow rate set at 3-4 litresper minute. The switches were then allowed to dry naturally at 25° C.and a relative humidity of 45 to 60%.

A control experiment was carried out without use of the conditioner, toobtain the background level of silicone present on the tip hairswitches.

The amount of silicone deposited on the hair samples was measured usingX-ray fluorescence spectrometry (measured in parts per million (ppm) ofsilicon).

Analysis Results

The tip deposition was calculated as (ppm silicon for test sample—ppmsilicon for control experiment). TABLE 2 Polaxamer or Tetronic TipDeposition Example Name x y x/y (Silicon ppm)  1 L44 10 21 0.48 344  2L64 13 30 0.43 342  3 P84 19 39 0.49 279  4 F77 52 35 1.49 310  5 F87 6139 1.56 286  6 F68 76 30 2.53 386  7 F88 103 39 2.64 549  8 F98 123 472.62 259  9 F108 132 56 2.36 394 10 T908 — — — 263 11 T1307 — — — 365 A— — — — 236 B L31 1 16 0.06 202 C P103 17 56 0.30 182 D F127 99 69 1.43134 E F38 42 16 2.63 222

1. An aqueous hair conditioner composition comprising: a) a cationicconditioning surfactant, b) discrete, dispersed droplets comprising awater-insoluble conditioning oil and c) a block copolymer with a meanmolecular weight of 1000 unified atomic mass units or more, comprisingpolyethyleneoxide and polypropyleneoxide blocks selected from the groupconsisting of (i) poloxamers according to formula I:

wherein the mean value of y is from 18 to 60 and the mean value x isfrom 7 to 140 such that the mean value of the ratio x/y is from 0.4 to3.0. and (ii) poloxamines according to formula II:

wherein the mean value of a is 2 or more and the mean value of b is 2 ormore.
 2. A composition according to claim 1 wherein the cationicconditioning surfactant is according to formula III:[N(R₁)(R₂)(R₃)(R₄)]⁺(X)⁻ wherein R₁, R₂, R₃, and R₄ are independentlyselected from (a) an aliphatic group of from 1 to 22 carbon atoms, or(b) an aromatic, alkoxy, polyoxyalkylene, alkylamido, hydroxyalkyl,alkoylalkyl, aryl or alkylaryl group having up to 22 carbon atoms; and Xis a salt-forming anion.
 3. A composition according to claim 1comprising from 0.01% to 5% by weight of the block copolymer.
 4. Acomposition according to claim 1 comprising from 0.01% to 10% by weightof the cationic conditioning surfactant.
 5. A composition according toclaim 1 comprising from 0.01% to 10% by weight of water-insolubleconditioning oil.
 6. A composition according to claim 1 wherein thewater-insoluble conditioning oil is a silicone conditioning oil.
 7. Acomposition according to claim 1 further comprising from 0.01 to 15% byweight of a fatty material selected from the group consisting of fattyalcohols, ethoxylated fatty alcohols, fatty acids and mixtures thereof.8. A process for making a composition: a) a cationic conditioningsurfactant, b) discrete, dispersed droplets comprising a water-insolubleconditioning oil and c) a block copolymer with a mean molecular weightof 1000 unified atomic mass units or more, comprising polyethyleneoxideand polypropyleneoxide blocks selected from the group consisting of (i)poloxamers according to formula l:

wherein the mean value of y is from 18 to 60 and the mean value x isfrom 7 to 140 such that the mean value of the ratio x/v is from 0.4 to3.0. and (ii) poloxamines according to formula II:

wherein the mean value of a is 2 or more and the mean value of b is 2 ormore; the process comprising: i) preparing a solution comprising waterand the block copolymer, ii) adding the water-insoluble conditioning oilto the solution, iii) forming the solution and the conditioning oil intoan oil-in-water emulsion, iv) dispersing the oil-in-water emulsioncomprising the block copolymer into a hair conditioner composition.
 9. Aprocess for making a composition comprising: a) a cationic conditioningsurfactant, b) discrete, dispersed droplets comprising a water-insolubleconditioning oil and c) a block copolymer with a mean molecular weightof 1000 unified atomic mass units or more, comprising polyethyleneoxideand polypropyleneoxide blocks selected from the group consisting of (i)poloxamers according to formula I:

wherein the mean value of v is from 18 to 60 and the mean value x isfrom 7 to 140 such that the mean value of the ratio x/v is from 0.4 to3.0. and (ii) poloxamines according to formula II:

wherein the mean value of a is 2 or more and the mean value of b is 2 ormore; the process comprising: i) preparing an oil-in-water emulsion of awater-insoluble conditioning oil, ii) dispersing the block copolymer inthe emulsion, iii) dispersing the oil-in-water emulsion comprising theblock copolymer into a hair conditioner composition.
 10. A method forenhancing deposition of water-insoluble conditioning oil from ahair-conditioner composition onto the hair tip region by applying to thehair the composition followed by rinsing with water, the compositioncomprising: a) a cationic conditioning surfactant, b) discrete,dispersed droplets comprising a water-insoluble conditioning oil and c)a block copolymer with a mean molecular weight of 1000 unified atomicmass units or more, comprising polyethyleneoxide and polypropyleneoxideblocks selected from the group consisting of (i) poloxamers according toformula I:

wherein the mean value of v is from 18 to 60 and the mean value x isfrom 7 to 140 such that the mean value of the ratio x/v is from 0.4 to3.0. and (ii) poloxamines according to formula II:

wherein the mean value of a is 2 or more and the mean value of b is 2 ormore.
 11. (canceled)